CA2008257A1 - Chemically modified proteins - Google Patents
Chemically modified proteinsInfo
- Publication number
- CA2008257A1 CA2008257A1 CA002008257A CA2008257A CA2008257A1 CA 2008257 A1 CA2008257 A1 CA 2008257A1 CA 002008257 A CA002008257 A CA 002008257A CA 2008257 A CA2008257 A CA 2008257A CA 2008257 A1 CA2008257 A1 CA 2008257A1
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- colorant
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- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/107—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides
- C07K1/1072—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides by covalent attachment of residues or functional groups
- C07K1/1077—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides by covalent attachment of residues or functional groups by covalent attachment of residues other than amino acids or peptide residues, e.g. sugars, polyols, fatty acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/107—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides
- C07K1/113—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length by chemical modification of precursor peptides without change of the primary structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Biophysics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Peptides Or Proteins (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
O.Z. 0050/40555 Abstract of the Disclosure: Chemically modified proteins obtainable by reacting casein, collagen, gelatin, albumin or mixtures thereof (a) with 0.5 to 15% by weight of chlorine or of a com-pound which liberates chlorine under the reaction conditions, in an aqueous medium at a pH of from O to 7 or (b) with 0.5 to 50% by weight of a non-aromatic mono- or disulfonic acid which contains in its organic radical one or more groups or structural feature which react with nucleophiles, in an aqueous medium at a pH of from 6 to 14, are used as dispersants in colorant formulations.
Description
2 ! O O ~ ~ ~ 7 O.Z. 0050/40555 Chemically modLfied proteins The present invention relates,to novel chemically modif ied proteins which can be obtained by reacting casein, c:ollas~en, gelatin and/or albumin ( a) with O . 5 to 15% by weight of chlorine or o~ a compound which liberates chlorine under the reaction condition~, in an aqueous medium at a pH of from 0 to 7 or (b~ with 0.5 ts 50% by weigh~ o~ ~ non--aromatic mono- or disulfonic acid which contain~ in i~ organic radical one or more group~ or ~tructural feature~
which react with nucleophile~, in an aqueou~ medium at a pH of from 6 to 14 to a proces~ for the preparation thereof, to the use thereof a~ dispersant~ in colorant formulation~ and to these formulations.
Di~per~ant~ conventionally u~ed for colorants, in : par~icular for vat and di~perse dye~, are ligninYulfon-ates, naphthalene~ulfonic acid~formaldehyde condensates or ~ulfonate~ of phenol/~ormaldehyde condensates. Norm-ally ~ery few of these are amenable to biological degra-dation or elimina~ion in clarification plant~ and they may therefore contribute to pollution of ~urface water~.
DE-A 27 34 204 de~cribe~ copolymers o~ styrene and acrylic acid in the ratio from 50s50 to 70s30 by weigh~ and o~ ~yrene, acrylic acld and maleic anhydride in tne ratio~ ~rom 50s40slO to 70s24:6 by weight in the ~on~ of water-~oluble ~alts a~ di~per~ nts ~or dyeæ.
The~e copolym~r~ are considarably le~8 enviro~mentally polluting than the abovementioned d~persant~ and, more-over, hava an acceptable di~per~ant action. N0vertheless, the dispersing propertie~ are:still in need of furthex improvement.
~xample~ of the u~e of naturally o~curring protein~ a~ protective colloidæ and di3persants have been di~clo#ed. ~hus, Athey in Tappi, VolO 58, ~o. 10 (1975) 55-61, de~cribe~ ~a~ein, inter alia, as a dispQrsant for , . .
, '.. ~
, , 20 ~825 ~
- 2 - O.~. OOS0/40555 pigments for paper coating. EP-B 018 947 relates to cas~in in the form of its ammonium salt as an emulsifier in the dyeing of polyest0r fabric. The naturally occur-ring proteins and their salt~ ara amenable to virtually S complete biological degradation or elimination, but their dispersant propertie~ in respect of colorant formula~ion~
are unsatisfactory, especially with regard to dispersion stability.
Hence the object of the present inven~ion was to provide dispersant which, while being amenable to virtu-ally complete biological degradation or elimination, have disper~ant properties which meet the high demands of colorant formulation~.
In accordance with thi~, we have found the chemically modified proteins defined in the introdurtion.
Of the protein~ which occur in animal bodies and which can be employed, casein (protein from milk~ is particularly important. It i~ also po~sible to use collagen (constituent of tendons, ligament~, ~kin, 20 cartilage and bone) and albumin (protein from egg~). It i5 likewi~e pos~ible to use gelatin which i~ obtained by partial hydrolysis of collagen (gelatin from skin or bone).
Reaation with 0.5 to 15% by weight, pre~rably 1 to 7% by wei~ht, of chlorine in embodiment ( ) i~ carried out in an aquaou~ solution or su~pen~ion o~ ~h~ protein at a pH o~ from 0 to 7, preferably 0 to S. It i~ u~ually carx~ed out at ~rom 20 to 100C, preferably rom 50 to 95C; however, the reaction can al~o be carried out above 100C under superatmospheric pressure. ~he acid~ which are norm~lly ~mployed are strong mineral acid~ ~uch a3 hydrochloric acid, sulfuric acid or ortho-phosphoric ~cido Be~ide~ elemental chlorine~ it i~ al~o pos~ible to employ in embodiment (a) compound~, or mixtures thereof, in an amount of from 0.5 to 15% by weight, preferably 1 to 7% by weight, whi~h liberate chlorine , ' : ' 2n~2~ t _ 3 O.Z. 0050/40555 under the reaction conditions. Suitable for this purpose are, for example, alkali metal salts of oxyacids o~
chlorine, such as hypochlorites or chlorate~, in acidic aqueous solution, or peroxo compound~ such a~ hydrsgen peroxide, sodium perborate and alkali metal or ammonium salts of peroxomono- and peroxodisulfuric acid in the presence of hydrochloric acid. The pH, the reaction temperature and the choice of acid~ which can be employed are the same a~ for the xeaction of the proteins with 1~ elemental chlorine.
After the protein~ havP been reacted with chlo-rine or a compound which libexates chlorine under the reaction conditions, the protein~ which have been chemio-ally modifie~ in thi~ way are conYerted into a form which is adequately soluble in water, preferably by adding a ba~e. The aqueous solutions obtained in this way u~ually have a pH of from 7 to 10. Bases which can be used are alkali metal or alkaline earth metal oxide-c or ~ydrox-ides, especially sodium or potas~ium hydroxide~ or amine~, especially alkanolamines such a~ mono-, di- or triethanolamine. It is al50 pos~ible to employ mixtures of the said bases.
The reaction of the proteins with 0.5 to 50% by weight, preferably 1 to 20~ by weight, o~ a non-aromatic mono- or disul~onic acid which con~ain~ in i~8 organic radical one or more groups or ~tructural foatu~e~ whlch react with nucle~phile~ takes place in embod~ment (b) in aqueous solution or ~u~pension at a p~l ~f ~rom 6 to 14, pre~erably 7 to 12. Examples of suitable gxQups or struc-tural features which can lead to an attack at nu~leophil-ic reaction center~ in the pro~eins are alkyl radicals, preferably C~-C4-alkyl radicals, which are ~ub~tituted by hydroxyl groups, which may be ~ulfat2d, or chlorine or bromine, a~ w~ll a~ the epoxy group and the 012finic double bond, pre~erably in the ~ position. Examples of ~uch mono- and disulfonio acid~ which may be mentioned axe hydroxymethanosulfonic acid, chloromethane~ulfonic - , : ........ . . .
~ , :
' :
20~2~7 _ 4 _ o.z. 005~/40555 acid, bromomethanesulfoniC acid, vinylsulfonic acid, 2-chloroethanesulonic acid, 2-bromoethane~ulfonic acid, ~-sulfoethyl sulfate, 3-chloro-2-hydroxypropane-1-sulfonic acid, 3-bromo-2-hydroxypropane-1-sulfonic acid~ 2,3 epo~ypropane-1-sulfonic acid and 1,2-dihydroxyethane-1,2-disulfonic acid. The sulfonic acids are preferably employed as alkali metal, alkaline earth metal, ~mmonium or amine salt~.
Before the reac~ion with the sulfonic acids as in ~b), the proteins are normally dis~olved, or at least partially dis~ol~ed, with the aid of base~, and the pH i~
adju~ted to the de~ired range. Base~ which can be employed are alkalL metal or alkaline earth mètal oxide~
or hydroxLdes, especially sodium or pota~iu~ hydroxide, ammonia or amine~, especially alkanolamines ~uch as mono-, di- or triethanolamine. It i~ al~o possibl0 to use mixtures of the said ba~es.
The re~ction of the protein~ with the sulfonic acids a~ in (b) i8 normally carried out at from 20 to 100C~ preferably from 50 to 95C; howaver, the reaction can al80 be carried out above lOO~C under superatmo3 pheric pressure.
The chemically modified protains according to the i~ention can be used in the ~onm o~ their aqueou~
801ution8, which aro usually ad~usted to a pH ~rom 7 to 10 a~er their pxepaxation, an~ have a low vi~co~ity o~, normally, 10 to 200 mPa.~, in a few ca~H~ up to 2,500 mPA.~, a~ 20C', or in ~olid ~orm a~ter ono of the conven-tlon~l method~ of working up, ~or example spray drying, free~æ drying or evaporation, as dispersant~ in solorant formulatlons.
The colorant formulation~ according to the in~ention are eithar anhydrous ~olids, which are u~ually in the form of powders, or stable aquaous di~p~r~ion~. By colorants are mQant dye~, for example textile dye~, and pigmant~ ~he dyes are usually ~ub~tance~ which are paringly ~oluble or in~oluble in water. Tha present ', '~
.. i 2~0~2~7 - 5 - O.Z. Oa50/40555 invention particularly relate~ to di~per~e dye~, vat dyes and optical brightener~. The ~aid typss of dyes include, in particular, r~presentatives o~ the classes of azo, anthraquinone and quinophthalone dyes.
The colorant foxmulation~ according to the invention contain 0.001 to 10 parts by weight, pr~ferably 0.1 to 2.5 part~ by weight, especially 0.7 to 2.2 parts by weight, in the case of solid formulations, and 0.001 to 2 parts by weight, preferably 0.05 to 1.5 parts by weight, especially 0.1 to 0.5 part by weight, in the casa of the liquid formulatîon~, of the chemically modified proteins per part by weight of the eolorant.
Particularly advantageou~ colorant formulation~
ara those which, be~ide~ the prot~in derivativa~ accord-ing to the invention, contain copolymer3 compQsed of olefinically unsaturated carboxylic acids and/or car-boxylic anhydride~ on the one handr and o~ water-insoluble monomer~ on the other hand, in the form of water-~oluble salts as additional di~persant These copolymers have been di~closed as dispersant~, for example in DE-A 27 34 204. Their disper~ant ac~ion is ba~ed on the principle that they have in the polymer molecule hydrophilic centers such a~ carboxyl~te groups in addition to hydrophobic polymer chains.
Particularly suitable copolymor~ of this type are composed, for example, of 30 to 50% by welght of acrylic acid and 50 to 70~ by weight o~ styrene or - 24 to 40% by weight of acrylic acid, 5 to 10~ by weight of maleic anhydride and 50 to 70~ by weight of styren~.
~he~e copolymer~ c~n be obtained by conventional method~
of free radical polymerization and are ~mployed in a ~orm which ha~ been completely or nearly completely neutraL-ized with alkali metal hydxoxidesl for example ~odium, pota~sium or llthium hydroxide, a~monia or alkanolamine~, for example triethanol~mine, triwn-propanolamine, 20~257 - 6 - o. æ . OG50/~0555 triisopropanolamine or tetra(hydroxypropyl)e~hylenedi-amine, in aqueous solution.
The colorant formulations according to the invention can contain the~e water-soluble salt~ of the copolymer~, or mixtures thereof, in an amount of up to 8 parts by weight, preferably up to 2 part~ by weight, especially up to 1.1 parts by weight, in the case of the solid formulations, and of up to 1.5 parts by weight/
preferably up to O.S part by weight~ e~pecially up to 0.15 part by weight, in the case of the liquid formula-tions, p~r part by weight of the colorant.
The liquid colorant formulation~ according to the inven~ion con~ain, beside~ the colorant and the dispers-ant, a~ a rule 20 to 100% by weight, based on the total amount of aqueou~ dispersion, of water or a mixture of water and water-retaining agent~. Water-retaining agents which can be u~ed are ethylen~ glycol, diethylen~ glycol, triethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, glycerol, sorbitol, dextrin, 2-butyne-1,4-diol or 2-methoxy-1-propanol.
Water-retaining agent~ prevent rapid dxying o~ thin film~
of the colorant dispersion.
The colorant formulations according ~o the in~ention can additionally contain small a~ount~, up to about 20% by weight based on the total colorant formula-tionr of th~ following auxiliarie~s - pre8er~atives (biocides~ to preven~ attack by bacteria`and fungi, for examplo p-chloro-~-cresol, 1,2-benzoi~othiazolin 3-one and chloroacetamide 0 - pH regulator~, especially buf~er mixtures contaLn-ing, for exampl~, alkali metal hydroxides, mono-~di- and triethanolam:ine, ~ulfuric acid, hydrochloric acid, phosphoric acid, ace~ic acid and ~he alkali me~al and ammonium ~al~A of the said acid~ 5 - antifoam agents for ~uppre~ing fo~m when milling the colorant fo~mulations and when using them for dyeing~ for example fatty alcohol~, fatty alcohol ` 2~2~7 _ 7 _ o.z, 0050/40555 alXoxylates, alkyl esters of carbo~ylic acid3 and phosphvric acid, as well as silicone-containing defoamers - viscosity regulators to improve the rheological behavior of colorant formulations, for example urea, N-methylacetamide, toluenesulfonate~, cumenesulfon-ates and naphthalen~sulfonat~ to reduce the viscos-ity and cellulose derivatives and polyacrylates to increase the viscosity 10 - wetting agent~ for improving the redispersibility o~
colorants in the form of powders and of films, for example alkyl sulfosuccinate~, dialkylsulfLmide~, alkyl phosphate~ and fatty alcohol alkoxylates - dustproofing agents ~o prevent th~ formation of dus~
when handling colorant formulations in the form of powders, especially mixture~ of an oily component and of a suitable emulsifier Yystem.
The colorant formulation3 according to the inv~ntion are produced in a conventional manner by milling and disper~ing the colorant, a~ a rule in an aqueou~ medium, for e~ample in kneader~ ball mi}l8, sand mill3, bead mill~ or a~tritor~, The colorant can be employed ~or thi~ in the form of a dry pewder or~ prefer-ably, in the form of the waker-~ontaining p~es8 cake produced in the preparation of the colorant. To produce the colorant ~ormulations in the ~orm o~ a pow~er accord-ing to th~ invention, the resulting aqueou~ colorant disper~iorl is, a~ a rule, spray-dr~ed in a conventional mar~e~, for ex~mple at from 60 to 160C.
~he colorant formulations aceordlng to the invention are ~uitable for :all ~yeing and printing proces~3.
The che~ically modified protein~ according to the i~vention, as well a~:th~ copolymer~ which ara to be used in combinakion with them and whi~h are compo~ed of, for example, ~tyrene, acrylic acid and mal~ic ~nhydrid~, are amen~bla to vir~ually complet~ biological degrada~ion or .
2~0~2~7 - 8 - O.Z. 0~50/40555 elLmination and thus do not pollute the environment. The biodegradability in the Zahn-Wellens test, defined by determining the chemical oxygen demand during the degra-dation process, is usually greater than 90% for bo h S classes of substances. By contrast, the ligninsulfonates, naphthalenesulfonic acid/formaldehyde condensates and sulfonates of phenol/formaldehyde conden~ate~ which are conventionally used as di~persant~ for colorant forma-tions mo~tly have degradabilities below 40~.
~ha chemically modified proteins according to the invention have a powerful dispersant action. The colorant di~persions produced with them are very finely divided and, at the same tLme, stable. The colorant formulation according to the invention have high thermal stability, ia. the colorant dispersion~ are very stable under the condition~ in the hot dyeing liquor In additionf formulation4 in the fonm of powders and ~olorant films are highly redispersible.
~nother advantage of tha chemically modified protein~ according to the invention i3 their light color.
Thu~ r when they are used as dL~persant~ in colorant formations, there is no longsr a risk that ad~acent fabric~ are s~ained during the dyeing of textlle~. Thi3 i8 important in ths case o~ brilliant color ~hades and, 2S espacially, when treating ~extiles with optical bright-ener~.
~ombination of ~he chAmlcally modified proteins accordin~ to the invention witht for ex~mple, the copoly-mers o~ styrene and acrylic acid, with or without mal~ic anhydride, di~closed in DE-A 27 34 204 re~ult~ in a further distinct improvement in the disper~ing power.
Thi~ is ~hown, especially, by the greater thermal stabil-ity and the longer shelf-life of these formulations. An additional advantage in thi~ ~onnection i8 the low tendency for dyes to migrate in continuou~ dyelng pro-ces~es, ie. the colors have a greater levelne~.
Unle~ stated otherwi e, the percentage~ in the 2~3~2~7 9 O.Z. 005~/40555 example~ relate to weight. The vi~cosities were measuxed in a rotary viscometer (Haake, Rotavisco) at 20C.
The biodegradability was determined by the Zahn-Wellens te~t de~cribed in DIN 38412 part 25. Thi~ te~t makes use of an activated sludge with a mixtura of various microorganisms and mineral nutrient~ for the biodegradation of the test substance. The ~queous solu-tion of the~e three components was aerated for a defined time ~up to 28 days) at a constant temperature of about 22C with substantial exclusion of light. The decrease in the amount of test substance wa~ mea~ured by determining the chemical oxygen demand.
The degradability measured in thi~ way was 38%
for a comm~rcial naphthalene~ulfonic acid/formaldehyde condensate and 33~ for a ligninsulfonatQ.
PREPARATI0~ EX~MPLES
Reaction of ca~ein with chlorine in hydrochloric acid 300 g of ca~ein were introduced a little at a time into a mixtur~ of 1,000 g of water and 90 g of 36%
strength hydrochloric acid at 65C. The su~pensien was stirred at 85 to 90C for 3 hours. Subsequently, at 60C
and a p~ o~ 9 to 1, 8.0 g o~ ga~eou~ chlorine (corre~-ponding to 2.7~ ba3ed on casein~ were pa~ed in within 45 minute~. ~he ~u~pen~lon was then stirred at 60C ~or 20 minute~ and 70C for 20 minute~. ~fter i~ had been cooled to room temperature, 98 g of 50% strength ~odiu~ hydxox-id~ 8elution were added to ~roduce a clear ~olution with a p~ o~ 7 . 5 and a viscosity o~ 18 mPa.s. The biodegrad-ability wa8 96%.
EXAMPL~ 2 Reaction of cas~in with ~odium hypochlorite in ~ulfuric acid 30~ g of casein were in~roduced ~ little a~ a time into a mixture o~ 1,500 g of water and 45 g of 96%
str2ngth sulfuric acid at 60C. The su~pQn~ion wa3 stirred at this temperature for 2 hours. Subsequ0ntly, at . ::~ '1 , . .
:,. ' ', ' ~ ' ~, ' :
7 200g~7 - 10 - O. Z . 0050/4~555 a pH of 0 to 1, 6 0 g of an aqueou sodium hypochlorite solution which contained 14% active chlorine (coxre~pond-ing to at least 5~9% NaOCl based on casein) were added dropwise at 60 to 70C wi~hin 30 minutes. The su~p2nsion was then stirred at 80C for 2 hour~. After cooling to room temperatur~, 100 g of 50% ~trenqth sodium hydroxide solution were added to adju~t to a pH of 8.5. The result-ing clear solution had a viscosity of 25 mPa.s.
Reaction of ca~ein with sodium chlorate in hydrochloric acid 200 g of casein were i~troduced a little at a tLme into a mixture of 915 g of water and 85 g of 36~
strength hydrochloric acid at 65 to 70C. The su~pen3ion was stirred at 80C for 3 hour~ and then, at a p~I of 0 ~o 1, a solution of 2.6 g of sodium chlorate (corre~ponding to 1.3% based on ca~ein) and 0.1 g of iron~ chloride hexahydrate in 4 g of water was a~ded all at onco, and the mixture wa~ stirred at 70C for 2 hours and then at 85C for 2 hours. After it had b~en cooled to room temperature, 92 g of S0% ~trength sodium hydroxide solution were added to produce a clear ~olution with a pH
o~ 8.5 and a visco~ity o~ 12 mPa.~.
Reaction of ca~ein wi~h sodium chlorato in sul~uric acid 200 g of casein were introduced a li~tle at a time into a m1xture of 1,000 g o~ water and 30 g of 96%
strength 3ul~uric acid a~ 60C. q'he ~u pen~ion was ~tlrred a~ 60 to 65C for 2 hour~ and then, a~ a pH of 0 to 1, 0.1 g of iron~III) chloride hexahydra~e and then 2.6 g of sodium chlorate (corresponding to 1.3% bs ed on ca~ein) dissolved in 4 g of water were added dropwi~e, and the mixture was stirred at 7a to 75C for 2 hour3 and at g0 to 95C for 4 hour~. After it had coolad to room temperature, 59 g of 50% ~trength ~odi~m hydroxida solu~ion was added to ad~ust to a pH of 8.5. The resul~-ing solution had a vi~cosity of 180 mPa.~O The biodegrad-~ 2~0~2~7 ~ O.Z~ 0050/40555 ability was 94%.
Reaction of casein with hydrogen peroxide in hydrochloric acid 200 g of casein were introduced a little at a time into a mixture of 1,000 g of water and 60 g of 36%
strength hydrochloric acid at 60 to 65C. ~he suspen~ion was stirred at this temperature for 2 hours. Sub~e-yuently, at 70C and a pH of O to 1, 8.3 g of 30%
~tr~ngth hydrogen peroxide (~orresponding to 1.2% anhyd-rous reagen~ based on casein~ were added dropwise within 20 minukes. The suspension was then stirred at 70~C for a further 2 hour~. After the mixture had been cooled to room temperature, 69 g of 50% ~trengt~ ~odium hydroxide solution were added to produce a clear solution with a pH
of 8.5 and a vi~cosity of 27 mPa. 3 . The biodegradability was 95%.
EXANP~E 6 Reaction of c sein with odium hydroxymethanesulfonate in sodium hydroxide ~olution 300 g of casein were introducsd a little at time into a mixture of 1,500 g of water and 54 g of 50~
s~reng~h ~odium hydroxide 801ution at 60~C and wers substantlally di3~01ved by stirring at thi~ temperature ~or one hour. To this solution, which had a p~ o~ 10.5, were ~dded dropwise, at the ~ame temperatura, 1~2 g of a 33~ ~trongth aqueous odium hydroxymethane ulfonate solution ~corresponding to 20.0~ anhydrou~ r~age~ ba~ed on ca~ein) within 30 minute~. ~he reaction mixture wa3 then ~tirred a~ 9~C for 3 hour~ The re~ulting ~olution had ~ pH of 9~5 and a visco~ity of 21 mPa.~. The biode-gradability wa~ 93~.
EXA~PLE 7 R~action o casein with sodium vinylsulfona~e in ~odium hydroxide solution 1,300 g of casein ware introduced a litgle at a time into a mlxtura of 3,500 g o~ wa~er and 25~ ~ of 50~
.
-.
.: , .
2~2~
- 12 - 0,Z. ~050/4~555 strength sodium hydroxide solution at 60C and were substantially dissolved by stirring at this temperature for one hour. To this solution, which had a pH of 8.5, were added dropwise, at the same temperature, 520 g of a S 25% strength aqueous sodium vinylsulfonate solution (corresponding to 10.0~ anhydrous reagent based on casein) within 1 hour. The reaction mixture was then stirred at 90C for 8 hours. After it had been cooled to room temparature, 45 g of 36% strength hydrochloric acid were added to ad~ust to a pH of 9. The resulting clear solution had a viscosity of 24 mPa.s. rhe biodegrad-ability was 90%.
BXA~PLE 8 Reaction of casein with sodium 3-chloro-2-hydroxypropane-l-sulfonate in sodium hydroxide solution 200 g of casein were introduced a little at a tLme into a mixture of 1,000 g of water and 36 g of 50%
strength sodium hydroxide solution at 60C and were substantially dis301ved by stirring at this temperature for one hour. The pH was then ad~usted to 10 with 50%
strsngth sodium hydroxide solution~ To this solution were added at 60C 10 g of sodium 3-chloro~2-hydroxypropane-l-sulfonate (corresponding to 5.0~ based on casein). The reaction mixture was then stixred at 80C for 2 hours~
~he resultlng clear solution had a pH of 11 and a visc03--ity of lS mPa.s.
Reaction of casein with disodium 1,2-dihydroxyethane-1,2-di~ulfonste in sodium hydroxide solution 200 g of casein were introduced a little at a tLme into a mixture of 1,000 g of water and 36 g of 50%
strsngth sodium hydroxide solution at 60C and were sub~tantially dissolved by stirring at this temperature for one hour, To this solution, which had a pH of 8.7, were added dropwise, at the ~ame temperature, 153 g of a 16% strength aqueous solution of disodium 1,2-dihydxoxy e~hane-1,2-disulfonate (corresponding to 12.2~ anh~drous 2 ~ 7 - 13 - O.Z. 0050/40555 reagent based on casein) within 0.7 hours. The reaction mixture wa then stirred at 90C for 3 hours. After it had been cooled to room temperature, the pH wa~ adjusted to 8 with a little 50% strength sodium hydroxide solu-S tion. The resulting cleax solution had a viscosity of 2,100 mPa.~. The biodegradability was 94%.
Copolymexs of styrene~ acxylic acid and maleic anhydride Copolymers of styrene and acrylic acid (Example 10) and styrene, acrylic acid a~d maleic anhydride (Examples ll to 14) were prepared as specified in DB-A 27 34 204. The terpolymer had a biodegradability of 95~. The copolymer was converted into a water-soluble salt by reaction with each of the base~ mentioned in Table 1 in an aqueou~ medium at about 60C. The degree of neutral-ization was lO0 mol-~ in each case. These solution~ had a solid~ content of from 20 ts 40~ and were used a~
additional di~per~ant~ for colorant foxmulation~.
20 Neutralized copolymers Example Compo~ition ~%) Ba~e No. Styrena Acrylic Maleic acid anhydrido triethanolamine 11 60 30 10 triethanolamine 12 60 30 10 tetra(hydro~ypropyl)-sthylenediamine 13 60 30 10 30dium hydroxide 14 60 30 lO lithium hydroxide _ .
USE E~AMPLES
The particls distribu~ion in the colorant disper-sion~ waQ characterized by the method of Richter an~
Vescia, ~elli nd Textilberichte (1965), No. 6, page~ 621-625. The numbers corre3pond ~o the p~rcentages of color-ant which ~ediment on centrifugation at l,000, 2~000 and 2~0 0f~2 5 7 - 14 - O.Z. 0050/40555 4,000 rpm after 5 minutes (firf3t 3 numkfer~ and which rff~main in the dispersion at tha end (4th number).
Colorantæ with small s~dimentation percentage~ and a high final p rcentage are particularly finely divided.
The sedimentation percentages from comparative tests with commercial naphthalenesulfonic acidJformalde-hyde condansate and ligninsulfonate are included in Tables 2 and 3 (Exampleff~f 46 to 51 and 66 to 70).
EXAMPLES 15 TO 45 ANfD COMPARATIVE EXAMP~E5 46 TO 51 Liquid colorant formulations The amounts specified in ~able 2, in each case based on the anhydrous substance, unles~f otharwise indicated, of colorant, which waf~f employed in the form of a press cake moist with water, and of disper3ants and auxiliaries were made into a paste by vig~rously stirring with water, with the total amount of the mixture being 1,OOfO g in each case. The mixture was then milled under the condition~ 3pecified in Table 2 (bead milling:
duration; f~fand miIlings numb~r of milling3 in which the mixture takes about 45 minutefs to pass through the mill) until a satiqffactorily fin2 dif3tribution, characterized by the ~fedimentation percentage~f, i9 achie~ed. The pH of the disper3ions was ad~fted to ~he indicated ~aluef in feach caff~fe by adding acetic ~cld or ff~fodium hydroxide solu~ion and was maintained during the milling.
EXAMPL~S 52 ~'0 65 AND COMæARA~IVE EXAMPLES 66 T0 70 Solid colorant formulations The amount~f ~pecified in Tableff 3, in efach case ba~ffud on th~f anhydrou3 ~fub3tancff, unle~fs i~dicated otherwi~fe, of colorant, which wa~f employed in thefformfof a pre~ cake moi~t with water, and of dispersants and, where appropriate, auxiliarie~ wer~ made into a pa~te by vlgorou~ly ~tirring with ahout 25% tEx~mples 5~-55 and 66), about 60% ~Examples 59-62, 68 and 69~ or 100%
(~xamples 5fi-58, 63-65, 67 and 70) of the to~al amoun~ of water required, wh~re the amoun~ o$ water reguired WA~
calculated on thfu baf3is of the f~olld~ content of the ., :
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20~257 - 15 - O~Z~ 0050/40555 dispersion before spray drying. The mixture was then milled at a pH of 8 to 9 in the case of colorant~ J and K or 10 to 11 in the case of colorant~ F, G and H under the conditions ~pecified in Table 3 (bead milling:
duration; sand milling: number of millings with the mixture taking about 45 minutes to pass through the mill) until a satisfactoxily fine distribution was achieved.
Subsequently, where appropriate, further amounts of disper~ant and the remaining water were added. These dispersions were spray-dried at the temperature indicated in Table 3 in each case. The percentage compo~itions of the colorant formulations are indicated in Table 3. The sedimen~ation percentages were determined after ~he re~ulting formulation~ in the form of pnwders had been resuspended in water.
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. ` ~ 2f~2~7 - 24 - O.Z. 0050/~0555 Meanings of abbre~iations in Table~ 2 and 3 The colorants employed are the following dyas listed in the Color Index:
A = Disperse Blue 60, C.I. 61100 (anthraquinone dye) S B = Disperse Red 91 (anthraquinone dye) C = DispArse Yellow 64, C.I. 47023 (hydro~yquinophthalone dye) D = Disper~ Blue 79, C.I. 11345 (azo dye) E - Fluore~cent Brightening Agen~ 199 ~erephthalic acid derivative~
F a Vat Blue 4, C.I. 69800 ~anthraquinone dye) G = Vat Blue 6, C.I. 69825 (anthraquinone dye~
H = Vat Green 1, C.I. 59825 (anthraquinone dye) J = Disperse Blue 330 (azo dye) R = Di~perse Red 167:1 (azo dye) The following auxiliarie~ were al~o used:
L = glycerol (as water-retaining agent) M = 1,2-benzoi~othiazolin-3-one (a~ biocide) in the form of a 9.5~ strength solution in water~propylene glycol N = ~orbitol (a3 water-retaining agent) Q = propylene glycol (as water-retaining agent~ :
R = ethylane glycol (a3 water-r~taining agent) ~ = triethan~lamine la~ pH regulator) U = sodium salt o di-Ca-C11-al~yl~ul~.~mide (as wetting agent~
The following type~ o milling were used:
P Y boad millin~
S - sand milling The following comme~cial di~per~ants were used for the comparative example3s X = naphthalenosulfonic acid/formald0hyde condensate (in the form of the ~odium salt) = ligninsulfona~e (in the form of the ~odium ~alt), ,. . .
- , .
: ' ;
which react with nucleophile~, in an aqueou~ medium at a pH of from 6 to 14 to a proces~ for the preparation thereof, to the use thereof a~ dispersant~ in colorant formulation~ and to these formulations.
Di~per~ant~ conventionally u~ed for colorants, in : par~icular for vat and di~perse dye~, are ligninYulfon-ates, naphthalene~ulfonic acid~formaldehyde condensates or ~ulfonate~ of phenol/~ormaldehyde condensates. Norm-ally ~ery few of these are amenable to biological degra-dation or elimina~ion in clarification plant~ and they may therefore contribute to pollution of ~urface water~.
DE-A 27 34 204 de~cribe~ copolymers o~ styrene and acrylic acid in the ratio from 50s50 to 70s30 by weigh~ and o~ ~yrene, acrylic acld and maleic anhydride in tne ratio~ ~rom 50s40slO to 70s24:6 by weight in the ~on~ of water-~oluble ~alts a~ di~per~ nts ~or dyeæ.
The~e copolym~r~ are considarably le~8 enviro~mentally polluting than the abovementioned d~persant~ and, more-over, hava an acceptable di~per~ant action. N0vertheless, the dispersing propertie~ are:still in need of furthex improvement.
~xample~ of the u~e of naturally o~curring protein~ a~ protective colloidæ and di3persants have been di~clo#ed. ~hus, Athey in Tappi, VolO 58, ~o. 10 (1975) 55-61, de~cribe~ ~a~ein, inter alia, as a dispQrsant for , . .
, '.. ~
, , 20 ~825 ~
- 2 - O.~. OOS0/40555 pigments for paper coating. EP-B 018 947 relates to cas~in in the form of its ammonium salt as an emulsifier in the dyeing of polyest0r fabric. The naturally occur-ring proteins and their salt~ ara amenable to virtually S complete biological degradation or elimination, but their dispersant propertie~ in respect of colorant formula~ion~
are unsatisfactory, especially with regard to dispersion stability.
Hence the object of the present inven~ion was to provide dispersant which, while being amenable to virtu-ally complete biological degradation or elimination, have disper~ant properties which meet the high demands of colorant formulation~.
In accordance with thi~, we have found the chemically modified proteins defined in the introdurtion.
Of the protein~ which occur in animal bodies and which can be employed, casein (protein from milk~ is particularly important. It i~ also po~sible to use collagen (constituent of tendons, ligament~, ~kin, 20 cartilage and bone) and albumin (protein from egg~). It i5 likewi~e pos~ible to use gelatin which i~ obtained by partial hydrolysis of collagen (gelatin from skin or bone).
Reaation with 0.5 to 15% by weight, pre~rably 1 to 7% by wei~ht, of chlorine in embodiment ( ) i~ carried out in an aquaou~ solution or su~pen~ion o~ ~h~ protein at a pH o~ from 0 to 7, preferably 0 to S. It i~ u~ually carx~ed out at ~rom 20 to 100C, preferably rom 50 to 95C; however, the reaction can al~o be carried out above 100C under superatmospheric pressure. ~he acid~ which are norm~lly ~mployed are strong mineral acid~ ~uch a3 hydrochloric acid, sulfuric acid or ortho-phosphoric ~cido Be~ide~ elemental chlorine~ it i~ al~o pos~ible to employ in embodiment (a) compound~, or mixtures thereof, in an amount of from 0.5 to 15% by weight, preferably 1 to 7% by weight, whi~h liberate chlorine , ' : ' 2n~2~ t _ 3 O.Z. 0050/40555 under the reaction conditions. Suitable for this purpose are, for example, alkali metal salts of oxyacids o~
chlorine, such as hypochlorites or chlorate~, in acidic aqueous solution, or peroxo compound~ such a~ hydrsgen peroxide, sodium perborate and alkali metal or ammonium salts of peroxomono- and peroxodisulfuric acid in the presence of hydrochloric acid. The pH, the reaction temperature and the choice of acid~ which can be employed are the same a~ for the xeaction of the proteins with 1~ elemental chlorine.
After the protein~ havP been reacted with chlo-rine or a compound which libexates chlorine under the reaction conditions, the protein~ which have been chemio-ally modifie~ in thi~ way are conYerted into a form which is adequately soluble in water, preferably by adding a ba~e. The aqueous solutions obtained in this way u~ually have a pH of from 7 to 10. Bases which can be used are alkali metal or alkaline earth metal oxide-c or ~ydrox-ides, especially sodium or potas~ium hydroxide~ or amine~, especially alkanolamines such a~ mono-, di- or triethanolamine. It is al50 pos~ible to employ mixtures of the said bases.
The reaction of the proteins with 0.5 to 50% by weight, preferably 1 to 20~ by weight, o~ a non-aromatic mono- or disul~onic acid which con~ain~ in i~8 organic radical one or more groups or ~tructural foatu~e~ whlch react with nucle~phile~ takes place in embod~ment (b) in aqueous solution or ~u~pension at a p~l ~f ~rom 6 to 14, pre~erably 7 to 12. Examples of suitable gxQups or struc-tural features which can lead to an attack at nu~leophil-ic reaction center~ in the pro~eins are alkyl radicals, preferably C~-C4-alkyl radicals, which are ~ub~tituted by hydroxyl groups, which may be ~ulfat2d, or chlorine or bromine, a~ w~ll a~ the epoxy group and the 012finic double bond, pre~erably in the ~ position. Examples of ~uch mono- and disulfonio acid~ which may be mentioned axe hydroxymethanosulfonic acid, chloromethane~ulfonic - , : ........ . . .
~ , :
' :
20~2~7 _ 4 _ o.z. 005~/40555 acid, bromomethanesulfoniC acid, vinylsulfonic acid, 2-chloroethanesulonic acid, 2-bromoethane~ulfonic acid, ~-sulfoethyl sulfate, 3-chloro-2-hydroxypropane-1-sulfonic acid, 3-bromo-2-hydroxypropane-1-sulfonic acid~ 2,3 epo~ypropane-1-sulfonic acid and 1,2-dihydroxyethane-1,2-disulfonic acid. The sulfonic acids are preferably employed as alkali metal, alkaline earth metal, ~mmonium or amine salt~.
Before the reac~ion with the sulfonic acids as in ~b), the proteins are normally dis~olved, or at least partially dis~ol~ed, with the aid of base~, and the pH i~
adju~ted to the de~ired range. Base~ which can be employed are alkalL metal or alkaline earth mètal oxide~
or hydroxLdes, especially sodium or pota~iu~ hydroxide, ammonia or amine~, especially alkanolamines ~uch as mono-, di- or triethanolamine. It i~ al~o possibl0 to use mixtures of the said ba~es.
The re~ction of the protein~ with the sulfonic acids a~ in (b) i8 normally carried out at from 20 to 100C~ preferably from 50 to 95C; howaver, the reaction can al80 be carried out above lOO~C under superatmo3 pheric pressure.
The chemically modified protains according to the i~ention can be used in the ~onm o~ their aqueou~
801ution8, which aro usually ad~usted to a pH ~rom 7 to 10 a~er their pxepaxation, an~ have a low vi~co~ity o~, normally, 10 to 200 mPa.~, in a few ca~H~ up to 2,500 mPA.~, a~ 20C', or in ~olid ~orm a~ter ono of the conven-tlon~l method~ of working up, ~or example spray drying, free~æ drying or evaporation, as dispersant~ in solorant formulatlons.
The colorant formulation~ according to the in~ention are eithar anhydrous ~olids, which are u~ually in the form of powders, or stable aquaous di~p~r~ion~. By colorants are mQant dye~, for example textile dye~, and pigmant~ ~he dyes are usually ~ub~tance~ which are paringly ~oluble or in~oluble in water. Tha present ', '~
.. i 2~0~2~7 - 5 - O.Z. Oa50/40555 invention particularly relate~ to di~per~e dye~, vat dyes and optical brightener~. The ~aid typss of dyes include, in particular, r~presentatives o~ the classes of azo, anthraquinone and quinophthalone dyes.
The colorant foxmulation~ according to the invention contain 0.001 to 10 parts by weight, pr~ferably 0.1 to 2.5 part~ by weight, especially 0.7 to 2.2 parts by weight, in the case of solid formulations, and 0.001 to 2 parts by weight, preferably 0.05 to 1.5 parts by weight, especially 0.1 to 0.5 part by weight, in the casa of the liquid formulatîon~, of the chemically modified proteins per part by weight of the eolorant.
Particularly advantageou~ colorant formulation~
ara those which, be~ide~ the prot~in derivativa~ accord-ing to the invention, contain copolymer3 compQsed of olefinically unsaturated carboxylic acids and/or car-boxylic anhydride~ on the one handr and o~ water-insoluble monomer~ on the other hand, in the form of water-~oluble salts as additional di~persant These copolymers have been di~closed as dispersant~, for example in DE-A 27 34 204. Their disper~ant ac~ion is ba~ed on the principle that they have in the polymer molecule hydrophilic centers such a~ carboxyl~te groups in addition to hydrophobic polymer chains.
Particularly suitable copolymor~ of this type are composed, for example, of 30 to 50% by welght of acrylic acid and 50 to 70~ by weight o~ styrene or - 24 to 40% by weight of acrylic acid, 5 to 10~ by weight of maleic anhydride and 50 to 70~ by weight of styren~.
~he~e copolymer~ c~n be obtained by conventional method~
of free radical polymerization and are ~mployed in a ~orm which ha~ been completely or nearly completely neutraL-ized with alkali metal hydxoxidesl for example ~odium, pota~sium or llthium hydroxide, a~monia or alkanolamine~, for example triethanol~mine, triwn-propanolamine, 20~257 - 6 - o. æ . OG50/~0555 triisopropanolamine or tetra(hydroxypropyl)e~hylenedi-amine, in aqueous solution.
The colorant formulations according to the invention can contain the~e water-soluble salt~ of the copolymer~, or mixtures thereof, in an amount of up to 8 parts by weight, preferably up to 2 part~ by weight, especially up to 1.1 parts by weight, in the case of the solid formulations, and of up to 1.5 parts by weight/
preferably up to O.S part by weight~ e~pecially up to 0.15 part by weight, in the case of the liquid formula-tions, p~r part by weight of the colorant.
The liquid colorant formulation~ according to the inven~ion con~ain, beside~ the colorant and the dispers-ant, a~ a rule 20 to 100% by weight, based on the total amount of aqueou~ dispersion, of water or a mixture of water and water-retaining agent~. Water-retaining agents which can be u~ed are ethylen~ glycol, diethylen~ glycol, triethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, glycerol, sorbitol, dextrin, 2-butyne-1,4-diol or 2-methoxy-1-propanol.
Water-retaining agent~ prevent rapid dxying o~ thin film~
of the colorant dispersion.
The colorant formulations according ~o the in~ention can additionally contain small a~ount~, up to about 20% by weight based on the total colorant formula-tionr of th~ following auxiliarie~s - pre8er~atives (biocides~ to preven~ attack by bacteria`and fungi, for examplo p-chloro-~-cresol, 1,2-benzoi~othiazolin 3-one and chloroacetamide 0 - pH regulator~, especially buf~er mixtures contaLn-ing, for exampl~, alkali metal hydroxides, mono-~di- and triethanolam:ine, ~ulfuric acid, hydrochloric acid, phosphoric acid, ace~ic acid and ~he alkali me~al and ammonium ~al~A of the said acid~ 5 - antifoam agents for ~uppre~ing fo~m when milling the colorant fo~mulations and when using them for dyeing~ for example fatty alcohol~, fatty alcohol ` 2~2~7 _ 7 _ o.z, 0050/40555 alXoxylates, alkyl esters of carbo~ylic acid3 and phosphvric acid, as well as silicone-containing defoamers - viscosity regulators to improve the rheological behavior of colorant formulations, for example urea, N-methylacetamide, toluenesulfonate~, cumenesulfon-ates and naphthalen~sulfonat~ to reduce the viscos-ity and cellulose derivatives and polyacrylates to increase the viscosity 10 - wetting agent~ for improving the redispersibility o~
colorants in the form of powders and of films, for example alkyl sulfosuccinate~, dialkylsulfLmide~, alkyl phosphate~ and fatty alcohol alkoxylates - dustproofing agents ~o prevent th~ formation of dus~
when handling colorant formulations in the form of powders, especially mixture~ of an oily component and of a suitable emulsifier Yystem.
The colorant formulation3 according to the inv~ntion are produced in a conventional manner by milling and disper~ing the colorant, a~ a rule in an aqueou~ medium, for e~ample in kneader~ ball mi}l8, sand mill3, bead mill~ or a~tritor~, The colorant can be employed ~or thi~ in the form of a dry pewder or~ prefer-ably, in the form of the waker-~ontaining p~es8 cake produced in the preparation of the colorant. To produce the colorant ~ormulations in the ~orm o~ a pow~er accord-ing to th~ invention, the resulting aqueou~ colorant disper~iorl is, a~ a rule, spray-dr~ed in a conventional mar~e~, for ex~mple at from 60 to 160C.
~he colorant formulations aceordlng to the invention are ~uitable for :all ~yeing and printing proces~3.
The che~ically modified protein~ according to the i~vention, as well a~:th~ copolymer~ which ara to be used in combinakion with them and whi~h are compo~ed of, for example, ~tyrene, acrylic acid and mal~ic ~nhydrid~, are amen~bla to vir~ually complet~ biological degrada~ion or .
2~0~2~7 - 8 - O.Z. 0~50/40555 elLmination and thus do not pollute the environment. The biodegradability in the Zahn-Wellens test, defined by determining the chemical oxygen demand during the degra-dation process, is usually greater than 90% for bo h S classes of substances. By contrast, the ligninsulfonates, naphthalenesulfonic acid/formaldehyde condensates and sulfonates of phenol/formaldehyde conden~ate~ which are conventionally used as di~persant~ for colorant forma-tions mo~tly have degradabilities below 40~.
~ha chemically modified proteins according to the invention have a powerful dispersant action. The colorant di~persions produced with them are very finely divided and, at the same tLme, stable. The colorant formulation according to the invention have high thermal stability, ia. the colorant dispersion~ are very stable under the condition~ in the hot dyeing liquor In additionf formulation4 in the fonm of powders and ~olorant films are highly redispersible.
~nother advantage of tha chemically modified protein~ according to the invention i3 their light color.
Thu~ r when they are used as dL~persant~ in colorant formations, there is no longsr a risk that ad~acent fabric~ are s~ained during the dyeing of textlle~. Thi3 i8 important in ths case o~ brilliant color ~hades and, 2S espacially, when treating ~extiles with optical bright-ener~.
~ombination of ~he chAmlcally modified proteins accordin~ to the invention witht for ex~mple, the copoly-mers o~ styrene and acrylic acid, with or without mal~ic anhydride, di~closed in DE-A 27 34 204 re~ult~ in a further distinct improvement in the disper~ing power.
Thi~ is ~hown, especially, by the greater thermal stabil-ity and the longer shelf-life of these formulations. An additional advantage in thi~ ~onnection i8 the low tendency for dyes to migrate in continuou~ dyelng pro-ces~es, ie. the colors have a greater levelne~.
Unle~ stated otherwi e, the percentage~ in the 2~3~2~7 9 O.Z. 005~/40555 example~ relate to weight. The vi~cosities were measuxed in a rotary viscometer (Haake, Rotavisco) at 20C.
The biodegradability was determined by the Zahn-Wellens te~t de~cribed in DIN 38412 part 25. Thi~ te~t makes use of an activated sludge with a mixtura of various microorganisms and mineral nutrient~ for the biodegradation of the test substance. The ~queous solu-tion of the~e three components was aerated for a defined time ~up to 28 days) at a constant temperature of about 22C with substantial exclusion of light. The decrease in the amount of test substance wa~ mea~ured by determining the chemical oxygen demand.
The degradability measured in thi~ way was 38%
for a comm~rcial naphthalene~ulfonic acid/formaldehyde condensate and 33~ for a ligninsulfonatQ.
PREPARATI0~ EX~MPLES
Reaction of ca~ein with chlorine in hydrochloric acid 300 g of ca~ein were introduced a little at a time into a mixtur~ of 1,000 g of water and 90 g of 36%
strength hydrochloric acid at 65C. The su~pensien was stirred at 85 to 90C for 3 hours. Subsequently, at 60C
and a p~ o~ 9 to 1, 8.0 g o~ ga~eou~ chlorine (corre~-ponding to 2.7~ ba3ed on casein~ were pa~ed in within 45 minute~. ~he ~u~pen~lon was then stirred at 60C ~or 20 minute~ and 70C for 20 minute~. ~fter i~ had been cooled to room temperature, 98 g of 50% strength ~odiu~ hydxox-id~ 8elution were added to ~roduce a clear ~olution with a p~ o~ 7 . 5 and a viscosity o~ 18 mPa.s. The biodegrad-ability wa8 96%.
EXAMPL~ 2 Reaction of cas~in with ~odium hypochlorite in ~ulfuric acid 30~ g of casein were in~roduced ~ little a~ a time into a mixture o~ 1,500 g of water and 45 g of 96%
str2ngth sulfuric acid at 60C. The su~pQn~ion wa3 stirred at this temperature for 2 hours. Subsequ0ntly, at . ::~ '1 , . .
:,. ' ', ' ~ ' ~, ' :
7 200g~7 - 10 - O. Z . 0050/4~555 a pH of 0 to 1, 6 0 g of an aqueou sodium hypochlorite solution which contained 14% active chlorine (coxre~pond-ing to at least 5~9% NaOCl based on casein) were added dropwise at 60 to 70C wi~hin 30 minutes. The su~p2nsion was then stirred at 80C for 2 hour~. After cooling to room temperatur~, 100 g of 50% ~trenqth sodium hydroxide solution were added to adju~t to a pH of 8.5. The result-ing clear solution had a viscosity of 25 mPa.s.
Reaction of ca~ein with sodium chlorate in hydrochloric acid 200 g of casein were i~troduced a little at a tLme into a mixture of 915 g of water and 85 g of 36~
strength hydrochloric acid at 65 to 70C. The su~pen3ion was stirred at 80C for 3 hour~ and then, at a p~I of 0 ~o 1, a solution of 2.6 g of sodium chlorate (corre~ponding to 1.3% based on ca~ein) and 0.1 g of iron~ chloride hexahydrate in 4 g of water was a~ded all at onco, and the mixture wa~ stirred at 70C for 2 hours and then at 85C for 2 hours. After it had b~en cooled to room temperature, 92 g of S0% ~trength sodium hydroxide solution were added to produce a clear ~olution with a pH
o~ 8.5 and a visco~ity o~ 12 mPa.~.
Reaction of ca~ein wi~h sodium chlorato in sul~uric acid 200 g of casein were introduced a li~tle at a time into a m1xture of 1,000 g o~ water and 30 g of 96%
strength 3ul~uric acid a~ 60C. q'he ~u pen~ion was ~tlrred a~ 60 to 65C for 2 hour~ and then, a~ a pH of 0 to 1, 0.1 g of iron~III) chloride hexahydra~e and then 2.6 g of sodium chlorate (corresponding to 1.3% bs ed on ca~ein) dissolved in 4 g of water were added dropwi~e, and the mixture was stirred at 7a to 75C for 2 hour3 and at g0 to 95C for 4 hour~. After it had coolad to room temperature, 59 g of 50% ~trength ~odi~m hydroxida solu~ion was added to ad~ust to a pH of 8.5. The resul~-ing solution had a vi~cosity of 180 mPa.~O The biodegrad-~ 2~0~2~7 ~ O.Z~ 0050/40555 ability was 94%.
Reaction of casein with hydrogen peroxide in hydrochloric acid 200 g of casein were introduced a little at a time into a mixture of 1,000 g of water and 60 g of 36%
strength hydrochloric acid at 60 to 65C. ~he suspen~ion was stirred at this temperature for 2 hours. Sub~e-yuently, at 70C and a pH of O to 1, 8.3 g of 30%
~tr~ngth hydrogen peroxide (~orresponding to 1.2% anhyd-rous reagen~ based on casein~ were added dropwise within 20 minukes. The suspension was then stirred at 70~C for a further 2 hour~. After the mixture had been cooled to room temperature, 69 g of 50% ~trengt~ ~odium hydroxide solution were added to produce a clear solution with a pH
of 8.5 and a vi~cosity of 27 mPa. 3 . The biodegradability was 95%.
EXANP~E 6 Reaction of c sein with odium hydroxymethanesulfonate in sodium hydroxide ~olution 300 g of casein were introducsd a little at time into a mixture of 1,500 g of water and 54 g of 50~
s~reng~h ~odium hydroxide 801ution at 60~C and wers substantlally di3~01ved by stirring at thi~ temperature ~or one hour. To this solution, which had a p~ o~ 10.5, were ~dded dropwise, at the ~ame temperatura, 1~2 g of a 33~ ~trongth aqueous odium hydroxymethane ulfonate solution ~corresponding to 20.0~ anhydrou~ r~age~ ba~ed on ca~ein) within 30 minute~. ~he reaction mixture wa3 then ~tirred a~ 9~C for 3 hour~ The re~ulting ~olution had ~ pH of 9~5 and a visco~ity of 21 mPa.~. The biode-gradability wa~ 93~.
EXA~PLE 7 R~action o casein with sodium vinylsulfona~e in ~odium hydroxide solution 1,300 g of casein ware introduced a litgle at a time into a mlxtura of 3,500 g o~ wa~er and 25~ ~ of 50~
.
-.
.: , .
2~2~
- 12 - 0,Z. ~050/4~555 strength sodium hydroxide solution at 60C and were substantially dissolved by stirring at this temperature for one hour. To this solution, which had a pH of 8.5, were added dropwise, at the same temperature, 520 g of a S 25% strength aqueous sodium vinylsulfonate solution (corresponding to 10.0~ anhydrous reagent based on casein) within 1 hour. The reaction mixture was then stirred at 90C for 8 hours. After it had been cooled to room temparature, 45 g of 36% strength hydrochloric acid were added to ad~ust to a pH of 9. The resulting clear solution had a viscosity of 24 mPa.s. rhe biodegrad-ability was 90%.
BXA~PLE 8 Reaction of casein with sodium 3-chloro-2-hydroxypropane-l-sulfonate in sodium hydroxide solution 200 g of casein were introduced a little at a tLme into a mixture of 1,000 g of water and 36 g of 50%
strength sodium hydroxide solution at 60C and were substantially dis301ved by stirring at this temperature for one hour. The pH was then ad~usted to 10 with 50%
strsngth sodium hydroxide solution~ To this solution were added at 60C 10 g of sodium 3-chloro~2-hydroxypropane-l-sulfonate (corresponding to 5.0~ based on casein). The reaction mixture was then stixred at 80C for 2 hours~
~he resultlng clear solution had a pH of 11 and a visc03--ity of lS mPa.s.
Reaction of casein with disodium 1,2-dihydroxyethane-1,2-di~ulfonste in sodium hydroxide solution 200 g of casein were introduced a little at a tLme into a mixture of 1,000 g of water and 36 g of 50%
strsngth sodium hydroxide solution at 60C and were sub~tantially dissolved by stirring at this temperature for one hour, To this solution, which had a pH of 8.7, were added dropwise, at the ~ame temperature, 153 g of a 16% strength aqueous solution of disodium 1,2-dihydxoxy e~hane-1,2-disulfonate (corresponding to 12.2~ anh~drous 2 ~ 7 - 13 - O.Z. 0050/40555 reagent based on casein) within 0.7 hours. The reaction mixture wa then stirred at 90C for 3 hours. After it had been cooled to room temperature, the pH wa~ adjusted to 8 with a little 50% strength sodium hydroxide solu-S tion. The resulting cleax solution had a viscosity of 2,100 mPa.~. The biodegradability was 94%.
Copolymexs of styrene~ acxylic acid and maleic anhydride Copolymers of styrene and acrylic acid (Example 10) and styrene, acrylic acid a~d maleic anhydride (Examples ll to 14) were prepared as specified in DB-A 27 34 204. The terpolymer had a biodegradability of 95~. The copolymer was converted into a water-soluble salt by reaction with each of the base~ mentioned in Table 1 in an aqueou~ medium at about 60C. The degree of neutral-ization was lO0 mol-~ in each case. These solution~ had a solid~ content of from 20 ts 40~ and were used a~
additional di~per~ant~ for colorant foxmulation~.
20 Neutralized copolymers Example Compo~ition ~%) Ba~e No. Styrena Acrylic Maleic acid anhydrido triethanolamine 11 60 30 10 triethanolamine 12 60 30 10 tetra(hydro~ypropyl)-sthylenediamine 13 60 30 10 30dium hydroxide 14 60 30 lO lithium hydroxide _ .
USE E~AMPLES
The particls distribu~ion in the colorant disper-sion~ waQ characterized by the method of Richter an~
Vescia, ~elli nd Textilberichte (1965), No. 6, page~ 621-625. The numbers corre3pond ~o the p~rcentages of color-ant which ~ediment on centrifugation at l,000, 2~000 and 2~0 0f~2 5 7 - 14 - O.Z. 0050/40555 4,000 rpm after 5 minutes (firf3t 3 numkfer~ and which rff~main in the dispersion at tha end (4th number).
Colorantæ with small s~dimentation percentage~ and a high final p rcentage are particularly finely divided.
The sedimentation percentages from comparative tests with commercial naphthalenesulfonic acidJformalde-hyde condansate and ligninsulfonate are included in Tables 2 and 3 (Exampleff~f 46 to 51 and 66 to 70).
EXAMPLES 15 TO 45 ANfD COMPARATIVE EXAMP~E5 46 TO 51 Liquid colorant formulations The amounts specified in ~able 2, in each case based on the anhydrous substance, unles~f otharwise indicated, of colorant, which waf~f employed in the form of a press cake moist with water, and of disper3ants and auxiliaries were made into a paste by vig~rously stirring with water, with the total amount of the mixture being 1,OOfO g in each case. The mixture was then milled under the condition~ 3pecified in Table 2 (bead milling:
duration; f~fand miIlings numb~r of milling3 in which the mixture takes about 45 minutefs to pass through the mill) until a satiqffactorily fin2 dif3tribution, characterized by the ~fedimentation percentage~f, i9 achie~ed. The pH of the disper3ions was ad~fted to ~he indicated ~aluef in feach caff~fe by adding acetic ~cld or ff~fodium hydroxide solu~ion and was maintained during the milling.
EXAMPL~S 52 ~'0 65 AND COMæARA~IVE EXAMPLES 66 T0 70 Solid colorant formulations The amount~f ~pecified in Tableff 3, in efach case ba~ffud on th~f anhydrou3 ~fub3tancff, unle~fs i~dicated otherwi~fe, of colorant, which wa~f employed in thefformfof a pre~ cake moi~t with water, and of dispersants and, where appropriate, auxiliarie~ wer~ made into a pa~te by vlgorou~ly ~tirring with ahout 25% tEx~mples 5~-55 and 66), about 60% ~Examples 59-62, 68 and 69~ or 100%
(~xamples 5fi-58, 63-65, 67 and 70) of the to~al amoun~ of water required, wh~re the amoun~ o$ water reguired WA~
calculated on thfu baf3is of the f~olld~ content of the ., :
.
.
. ~ ' .
20~257 - 15 - O~Z~ 0050/40555 dispersion before spray drying. The mixture was then milled at a pH of 8 to 9 in the case of colorant~ J and K or 10 to 11 in the case of colorant~ F, G and H under the conditions ~pecified in Table 3 (bead milling:
duration; sand milling: number of millings with the mixture taking about 45 minutes to pass through the mill) until a satisfactoxily fine distribution was achieved.
Subsequently, where appropriate, further amounts of disper~ant and the remaining water were added. These dispersions were spray-dried at the temperature indicated in Table 3 in each case. The percentage compo~itions of the colorant formulations are indicated in Table 3. The sedimen~ation percentages were determined after ~he re~ulting formulation~ in the form of pnwders had been resuspended in water.
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. ` ~ 2f~2~7 - 24 - O.Z. 0050/~0555 Meanings of abbre~iations in Table~ 2 and 3 The colorants employed are the following dyas listed in the Color Index:
A = Disperse Blue 60, C.I. 61100 (anthraquinone dye) S B = Disperse Red 91 (anthraquinone dye) C = DispArse Yellow 64, C.I. 47023 (hydro~yquinophthalone dye) D = Disper~ Blue 79, C.I. 11345 (azo dye) E - Fluore~cent Brightening Agen~ 199 ~erephthalic acid derivative~
F a Vat Blue 4, C.I. 69800 ~anthraquinone dye) G = Vat Blue 6, C.I. 69825 (anthraquinone dye~
H = Vat Green 1, C.I. 59825 (anthraquinone dye) J = Disperse Blue 330 (azo dye) R = Di~perse Red 167:1 (azo dye) The following auxiliarie~ were al~o used:
L = glycerol (as water-retaining agent) M = 1,2-benzoi~othiazolin-3-one (a~ biocide) in the form of a 9.5~ strength solution in water~propylene glycol N = ~orbitol (a3 water-retaining agent) Q = propylene glycol (as water-retaining agent~ :
R = ethylane glycol (a3 water-r~taining agent) ~ = triethan~lamine la~ pH regulator) U = sodium salt o di-Ca-C11-al~yl~ul~.~mide (as wetting agent~
The following type~ o milling were used:
P Y boad millin~
S - sand milling The following comme~cial di~per~ants were used for the comparative example3s X = naphthalenosulfonic acid/formald0hyde condensate (in the form of the ~odium salt) = ligninsulfona~e (in the form of the ~odium ~alt), ,. . .
- , .
: ' ;
Claims (12)
1. A chemically modified protein obtainable by reacting casein, collagen, gelatin, albumin or mixtures thereof (a) with 0.5 to 15% by weight of chlorine or of a com-pound which liberates chlorine under the reaction conditions, in an aqueous medium at a pH of from 0 to 7 or (b) with 0.5 to 50% by weight of a non-aromatic mono- or disulfonic acid which contains in its organic radical one or more groups or structural features which react with nucleophiles, in an aqueous medium at a pH of from 6 to 14.
2. A chemically modified protein as claimed in claim 1, obtainable by reaction of casein.
3. A chemically modified protein as claimed in claim 1, obtainable by reaction in method (a) with 1 to 7% by weight of chlorine or of a compound which liberates chlorine under the reaction conditions.
4. A chemically modified protein as claimed in claim 1, obtainable by reaction in method (a) at a pH of from 0, to 5.
5. A chemically modified protein as claimed in claim 1, obtainable by reaction in method (b) with 1 to 20% by weight of a non-aromatic mono- or disulfonic acid which contains in its organic radical one or more groups or structural features which react with nucleophiles.
6. A chemically modified protein as claimed in claim 1, obtainable by reaction in method (b) at a pH of from
7 to 12.
7. A process for the preparation of a chemically modified protein as claimed in claim 1, which comprises reacting casein, collagen, gelatin, albumin or mixtures thereof (a) with 0.5 to 15% by weight of chlorine or of a com-pound which liberates chlorine under the reaction conditions, in an aqueous medium at a pH of from 0 to - 26 - O.Z. 0050/40555 7 or (b) with 0.5 to 50% by weight of a non-aromatic mono- or disulfonic acid which contains in its organic radical one or more groups or structural features which react with nucleophiles, in an aqueous medium at a pH of from 6 to 14.
7. A process for the preparation of a chemically modified protein as claimed in claim 1, which comprises reacting casein, collagen, gelatin, albumin or mixtures thereof (a) with 0.5 to 15% by weight of chlorine or of a com-pound which liberates chlorine under the reaction conditions, in an aqueous medium at a pH of from 0 to - 26 - O.Z. 0050/40555 7 or (b) with 0.5 to 50% by weight of a non-aromatic mono- or disulfonic acid which contains in its organic radical one or more groups or structural features which react with nucleophiles, in an aqueous medium at a pH of from 6 to 14.
8. A process for the dispersion of colorants in colorant formulations, which comprises using for this purpose a chemically modified protein as claimed in claim 1.
9. A solid anhydrous or liquid aqueous colorant formulation containing as dispersant a chemically modi-fied protein as claimed in claim 1.
10. A solid anhydrous colorant formulation as claimed in claim 9, containing 0.001 to 10 parts by weight of the dispersant per part by weight of the colorant.
11. A liquid aqueous colorant formulation as claimed in claim 9, containing 0.001 to 2 parts by weight of the dispersant per part by weight of the colorant.
12. A colorant formulation as claimed in claim 9, containing as additional disperant water-soluble salts of copolymers composed of olefinically unsaturated carboxylic acids, carboxylic anhydrides or mixtures thereof on the one hand, and of water-insoluble monomers on the other hand.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3903362A DE3903362A1 (en) | 1989-02-04 | 1989-02-04 | CHEMICALLY MODIFIED PROTEINS |
| DEP3903362.7 | 1989-02-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2008257A1 true CA2008257A1 (en) | 1990-08-04 |
Family
ID=6373447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002008257A Abandoned CA2008257A1 (en) | 1989-02-04 | 1990-01-22 | Chemically modified proteins |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5124438A (en) |
| EP (1) | EP0382054B1 (en) |
| JP (1) | JPH02235900A (en) |
| AT (1) | ATE121751T1 (en) |
| CA (1) | CA2008257A1 (en) |
| DE (2) | DE3903362A1 (en) |
| DK (1) | DK0382054T3 (en) |
| ES (1) | ES2070936T3 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733463A (en) * | 1992-07-24 | 1998-03-31 | Peach State Labs, Inc. | Lowering the pH with an acid/base salt as a pH adjusting agent |
| US5234466A (en) * | 1992-07-24 | 1993-08-10 | Peach State Labs, Inc. | Lowering of the pH of textile processing solutions by adding urea sulfate as a pH adjusting agent |
| US7029553B1 (en) | 1992-07-24 | 2006-04-18 | Peach State Labs, Inc. | Urea sulfate and urea hydrochloride in paper and pulp processing |
| US6454787B1 (en) | 1998-12-11 | 2002-09-24 | C. R. Bard, Inc. | Collagen hemostatic foam |
| US6361551B1 (en) | 1998-12-11 | 2002-03-26 | C. R. Bard, Inc. | Collagen hemostatic fibers |
| US6524492B2 (en) | 2000-12-28 | 2003-02-25 | Peach State Labs, Inc. | Composition and method for increasing water and oil repellency of textiles and carpet |
| US20050054752A1 (en) * | 2003-09-08 | 2005-03-10 | O'brien John P. | Peptide-based diblock and triblock dispersants and diblock polymers |
| US7538187B2 (en) * | 2005-08-01 | 2009-05-26 | E. I. Du Pont De Nemours And Company | Coloring compositions with peptide-based dispersants and binders |
| US8481678B2 (en) | 2009-03-30 | 2013-07-09 | E I Du Pont De Nemours And Company | Peptide-based tooth whitening reagents |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2373602A (en) * | 1945-04-10 | Proteinaceous surface active agents | ||
| GB213536A (en) * | 1923-03-29 | 1924-09-04 | Albert Mendel Ag | A process for producing halogen-albumin-compounds |
| US2304308A (en) * | 1939-06-24 | 1942-12-08 | Rohm & Haas | Dispersible composition |
| JPS5071700A (en) * | 1973-11-06 | 1975-06-13 | ||
| DE2734204C3 (en) * | 1977-07-29 | 1980-02-14 | Basf Ag, 6700 Ludwigshafen | Aqueous, flowable, dispersion-stable preparations |
| EP0018947B1 (en) * | 1979-05-04 | 1984-02-01 | Ciba-Geigy Ag | Dyeing composition and processes for dyeing fabrics made of polyester or a polyester blend with cotton or wool |
| DE3228479A1 (en) * | 1982-07-30 | 1984-02-09 | Dénes 7312 Kirchheim Pötschke | DETERGENT FOR TEXTILES |
| US4494994A (en) * | 1983-03-28 | 1985-01-22 | Seton Company | Surface active agent compositions containing polypeptides and lignin sulfonic acid |
| FR2614896B1 (en) * | 1987-05-05 | 1989-09-01 | Rech Innovation | CASE-BASED PLASTICS AND THEIR PREPARATION |
-
1989
- 1989-02-04 DE DE3903362A patent/DE3903362A1/en not_active Withdrawn
-
1990
- 1990-01-12 US US07/464,196 patent/US5124438A/en not_active Expired - Fee Related
- 1990-01-22 CA CA002008257A patent/CA2008257A1/en not_active Abandoned
- 1990-01-30 AT AT90101790T patent/ATE121751T1/en not_active IP Right Cessation
- 1990-01-30 DK DK90101790.5T patent/DK0382054T3/en active
- 1990-01-30 DE DE59008952T patent/DE59008952D1/en not_active Expired - Fee Related
- 1990-01-30 ES ES90101790T patent/ES2070936T3/en not_active Expired - Lifetime
- 1990-01-30 EP EP90101790A patent/EP0382054B1/en not_active Expired - Lifetime
- 1990-02-05 JP JP2024579A patent/JPH02235900A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0382054A2 (en) | 1990-08-16 |
| ES2070936T3 (en) | 1995-06-16 |
| EP0382054A3 (en) | 1991-11-13 |
| JPH02235900A (en) | 1990-09-18 |
| ATE121751T1 (en) | 1995-05-15 |
| DK0382054T3 (en) | 1995-07-03 |
| DE59008952D1 (en) | 1995-06-01 |
| DE3903362A1 (en) | 1990-08-09 |
| EP0382054B1 (en) | 1995-04-26 |
| US5124438A (en) | 1992-06-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |